Water insoluble azodyestuff



Patented Aug. 8, 1933 UNITED STATES PATENT OFFICE 7 1,921,362. WATERINSOLUBLE AZODYESTUFF Leopold Laska, Arthur Zitscher, and Wilhelm Koch,Offenbach-on-the-Main, Germany, as-

' signors to General Aniline Works, Inc., New

' York, N. Y., a Corporation of Delaware No Drawing.

No. 387,801, and in 192s 10 Claims.

Our present invention relates to new waterinsoluble azodyestuffs of theprobable general formula:

NO: OH

0 O-N H-aryl in which formula the benzene nuclei may contain furthermonovalent substituents, such as a further nitro group, halogen, methylor alkoxy. They'are obtained by combining a diazotized compound of thediphenylamine series of the general formula: v v

wherein the benzene nuclei may-contain further monovalent substituents,such as a further nitro Application August 22, 1929, Serial GermanySeptember 11,

so-called Turkey-chocolates of the oriental countries. It is surprisingthat some of the dyeings produced by the present method are remarkablyfast tokier boiling.

Example 1 Well boiled and dried cotton yarn is impregnated with asolution containing per liter 4 grs. of2.3-hydroxynaphthoyl-4-chloroaniline, 10 com. of Turkey red oil, and 8com. of a caustic soda solution of 34 B., well'wrung out and developedin a diazo solution, which is neutralized with sodium bicarbonate,containing 2.7 grs.

of 4 amino 3'-chloro--6--nitro-diphenylamine,

rinsed and soaped.

In this manner a very dark garnet-brown dyeing of very satisfactoryfastness to kier boiling is obtained.

The dyestufi thus produced-on the fiber corresponds probably totheformula:

group, halogen, methyl or alkoxy, with any arylamide of2.3-hydroxynaphthoic acid not containimportance esp eciallyfor theproduction of the Example 2 Cotton yarn previously treated in the usualmanner is impregnated with a solution containing per liter 2.5 grsfiof,2.3-hydroxynaphthoyl-2- naphthylamine,- 100cm. ofiTurkey. red oil, and7.5 ccm. of a causticsoda solution of 34 B., well wrung out anddeveloped in a diazo solution, which is neutralized with sodiumbicarbonate, containing 2.8 grs. of 4-amino-2.4'-dinitro-diphenylamineper liter and worked up as usual.

In this manner a dark garnet dyeing of very good fastness'is obtained. 7

The dyestufi' thus produced on the fiber corresponds probably to theformula:

Example 3 Cotton yarn is, after the customary preliminary treatment,impregnated with a solution containing per liter 5 grs. of2.3-hydroxynaphthoyll-anisidine, 10 com. of Turkey red oil, and 15 com.of a caustic soda solution of 34 Be, well wrung out and then developedin a neutralizeddiazo solution containing 3.5 grs. of 4-amino-2.5-dich1oro-2.4-dinitrodiphenylamine per liter and worked up in thecustomary manner.

A garnet-brown dyeing of good fastness to light is obtained.

The dyestuff thus produced on the fiber corresponds probably to theformula:

pomnO-oorn.

The process may be carried out in the same manner with other compoundsof the diphenylamine series substituted as in the above general formulawith a intro-group in the o-position to the imino-gr'oup and with otherarylide's of 2.3- hydroxynaphthoic acid.

In the following table there are cited some further components suitablefor the combination according to our process and the shadesof dyeingsobtained by the production of the dyestufls onthe fiber:

Diem-compound of Combined with Shade of dyeing obtained 4 amino 2nitrodlphenylarnine'. I aniline.

Do 2.3 hydroxynaphthoylo an'is'idine.

Do 2.3 hydroxynaphthoyl- 2 amino 5 chloro 1 methyl-benzene.

Do 2.3 T hydroxynaphthoyl- 2 amino 5 chloro-hydroquinonedimethylether.

Do 2.3 hydroxyn'aphthoylf-naphthylamine.

4 amino 3 chloro- 2.3 hydroxy'naphthoyl 6 m'tro dip'henylp-phenetidine.

ainine.

Do 2.3 hydroxynaphthoyl p-chl0r0-anillne.

Do 2.3 hydroxynaphthoyl 25: aminohydro'quinonedimethylether.

Do 2.3 hydroxynaphthoyl 5 amino- 2 7 methoxy l-rnethylbenzene.

Do 2.3 hydroxynaphthoyl V l-naphthylamine.

Do 2.3 hydroxynaphthoyl 2-naphthylamine. Do 2.3 hYGmXyn'aphthoyI4-amino-2.5-dimethyl- 3' ehloro 6' nitrodiphenylamine.

4 amino 2.4- dinitro-diphcnylamine.

2.3 hydroxynaphthoyl- 2 amino 3 naphtholmethylether.

2.3 hydroxynaphth'oyl otoluidine.

2.3 hydroxynaphthoylhydroquinonedimethylethe 2.3 hydroxynaphthoyl 5amino 2 mothoxy 1- methylbenzene.

Dark

2 amino- 4 -'chloro I Blacl'zish garnetbrown. D o

D a r k brown. Brown garnet.

garnetgarnetbrown.

Brownish garnet.

Garnet-brown.

D a r k garnetmown. Brownish garnet.

Garnet.

Brownish garnet.

Q Shade of dyeing Diazo compound of Combined with Obtained 4-an1ino-2.4-linltro-' 2.3 hydroxynaphthoyl Red-brown.

diphenylamine. 1-naphthylamine.

4 amino- 3-methyl- 2.3 hydroxynaphthoyl Bluish garnet.

2.4-dinitro-diphe- 6 amino 3 methoxy nylamine. l-methylbenzene.

Do 2.3 hydroxynaphthoyl Do.

l-naphthylainine. Do 2.3 hydroxynaphthoyl Do.

2-naphthylamine. 4-amino-3-methoxy- 2.3 hydroxynaphthoyl Dark bluishgar- 2.4 diIlitI'OdiDhB-t p-anisidine. net. nylamine 0-- 2.3-hydroxynaphthoyl Irongarnet. m-nitroaniline. Do 2.3 hydroxynaphthoylVioletish brown.

' 2 amino 5 chloro hydroquinonedimethe. er.

4 amino 3 ehloro 2.3 hydroxynephthoyl Garnet.

2C4. dinitro dianiline. phenylamine.

Do 2.3 hydroxynaphthoyl Brownish claret.

o-toluidine. Do 2.3 hydroxynaphthoyl Garnet.

6 amino 3 methoxy l-methylbenzene. Do 2.3 hydroxynaphthoyl Bluishgarnet;- l-naphthylamine. Do. (2 mo]. probis 2.3-hydroxynaph-Reddish-brown. portions.) thoyl-dianisidine. p 4-arnino-25 -dichloro-2.3 hydroxy-naphthoyl- Full red-brown. 2i

2.4-dinitro-diphcniline. I00 nylamine.

Do 2.3 hydroxynaphthoyl Red-brown.

p-phenetidine. Do 2.3 bydroxynaphthoyl Do.

2 aminohydroquinonedimethylether. Do 2.3 hydroxynaphthoyl Do. 6

5 amino 2 methoxy l-methylbenzene. Do 2.3 hydroxynaphthoyl Do.

In-nitroaniline'. Do 2.3 hydroxynaphthoyl Brownish garnet.

Z-naphthylamine.

4 amino 3 nitro 2.3 hydroxynaphthoyl Garnet. T

2.4-dinitro-dipheo-anisidine. I10 nylamine.

Do 2.3 hydroxynaphthoyl Bluish garnet.

- 2 aminohydroquinone- V dimethylether.

Do 2.3 hydroxynaphthoyl Brownish garnet.

2-ann'no-5-chloro- M hydroquinonedimethyl- 5 her. 11 Do 2.3hydroxynaphthoyl Garnet.

6 amino- 3 methoxy l-methylbenzene. Do 2.3 hydroxynaphthoyl Do.

2 -2T;]i"l11iIl01;5 chloro l me oxy enzene. 20

We claim: 1. As new compounds azodyestufis corresponding probably to thegeneral formula:

\ N02 s -0H O \7 O NH aryl,

in which formula the benzene nuclei may contain alkyl, alkoxy, nitro orhalogen, which 'dye stuffs yield color lakes, when mixed with the usualsubstratayand dyeings, when produced on the vegetable fiber according tothe ice-color methods, the color lakes and dyeings being distinguishedby 7 dark garnet to garnet-brown shades.

2. As new compounds azodyestufis corresponding probably to the generalformula:

l r: NO: in OH 1 O0'NHaryl,

iso

nitro group may contain a chlorine atom or a further nitro group, whichdyestufis yield color lakes when mixed with the usual substrata anddyeings when produced on the vegetable fiber according to the ice-colormethods, the color lakes and dyeings being distinguished by dark garnetto garnetbrown shades.

3. As new compounds azodyestuffs correspond ing probably to the generalformula:

' 4. As new compounds azodyestuifs corresponding probably to the generalformula:

01 NOrQNHQ-N=N OH I GONH-aryl,

which dyestuffs yield color lakes and dyeings of dark garnetto'garnet-brown shades.

5.'As a new compound the azodyestuff corresponding probably to theformula:

' group may contain a chlorine atom or a further nitro group, saiddyestuffs yielding color lakes, when mixed with the usual substrata, anddye-' ings, when produced on vegetable fiber according to ice-colormethods, the color lakes and dyeings. being distinguished by dark garnetto-garnet-brown shades.

' '7. As a new compound the azodyestufi corresponding probably to theformula:

on (JO-NH-Obl which dyestuff yields color lakes and dyeings of a verydark garnet-brown shade and satisfactory fastness to kier boiling.

' 8. The method of making an azo dye which comprises coupling diazotized4-amino-2.4-dinitro-diphenylamine with an arylide of2.3-hydroxynaphthoic acid.

9 As a new product, an azo dye having the general formula wherein Rrepresents a residue of the benzene or naphthalene series. v

10. As new compounds azo dyestuffs corresponding to the general formula:

which dyestufi' yields color lakes and dyeings of in' which formula thebenzene nuclei may be garnet-brown shade and good fastness to light.

6. As new compounds, azodyestuffs corresponding probably to the generalformula:

02 on (Sonia-w in whichformula the nucleus bearing the nitro furthersubstituted by 'alkyl, nitro or halogen groups. 1 LEOPOLD LASKAV WILHELMKOCH.

